text:
|Publication number
|Publication type
|Application number
|Publication date
|12 Oct 1993
|Filing date
|27 Feb 1991
|Priority date
|22 Mar 1990
|Fee status
|Also published as
|Publication number
|Albin F. Turbak, Rodney A. Smith, Chung-Hsien Zah
|Original Assignee
|Interface, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Non-Patent Citations (5), Referenced by (30), Classifications (9), Legal Events (9)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation-in-part of application Ser. No. 07/497,893, filed Mar. 22, 1990, now abandoned.
This invention is a method to impart permanent stain resistance to polyamide fibers.
Polyamide fibers are found in a wide variety of commercially important textile materials, including nylon, silk, wool, and leather. It is estimated that 75% of all carpet currently produced in the United States, and 46% of all carpet produced in Europe, is prepared from nylon fiber. Nylon fiber is also used extensively in upholstery and fabric coverings.
One disadvantage in using nylon, as well as other polyamide fibers, as the pile yarn in carpet or as a constituent in fabric is that the fiber is easily stained by many materials. In fact, it has been determined that more carpets are replaced because of staining than because the fibers are worn. The most significant mechanism of action of staining of nylon fiber appears to involve the formation of ionic bonds between protonated terminal amine groups on the polyamide fiber and anionic materials such as acid dyes. Common substances that contain acid dyes include mustard, wine, and soft drinks that contain FD&C red dye No. 40 (such as cherry Kool Aid�).
The most common approach to increasing the resistance to staining of polyamide fibers has been to treat the fibers with a colorless formaldehyde aromatic condensation polymer that has sulfonate groups on the aromatic rings. The condensation polymers are typically prepared from 4,4'-dihydroxydiphenylsulfone (also referred to as 4,4'-sulfonylbisphenol or DDS), phenyl 4-sulfonic acid, naphthalene sulfonic acid or 2,4-dimethylbenzene sulfonic acid. The sulfonate groups ionically bond to available protonated amino groups in the polyamide fiber, preventing the protonated amino groups from later bonding to commonly used acid dyes.
Examples of methods to impart stain resistance to nylon fibers that include the use of a sulfonated condensation polymer are described in U.S. Pat. No. 4,839,212 to Blythe (disclosing nylon carpet fibers, coated with a sulfonated aromatic condensation polymer, that resist staining by acid dyes at room temperature but are dyeable at elevated temperatures); U.S. Pat. No. 4,501,591 to Ucci, et al. (disclosing the use of sulfonated phenol-formaldehyde condensation polymers in combination with alkali metal silicates to impart stain resistance to nylon fibers); and U.S. Pat. Nos. 4,592,940 and 4,680,212 to Blythe, et al. (disclosing formaldehyde condensation products formed from a mixture of sulfonated dihydroxydiphenylsulfone and phenylsulphonic acid, wherein at least 40% of the repeating units contain an --SO3 X radical, and at least 40% of the repeating units are dihydroxydiphenylsulfone).
U.S. Pat. No. 4,699,812 to Munk discloses a method for imparting stain resistance to nylon fibers that includes applying a solution of an aliphatic sulfonic acid containing 8 to 24 carbon atoms under acidic conditions.
In a variation of these methods, the sulfonated formaldehyde condensation polymers have been blended with other polymers to increase the effectiveness of stain resistance. For example, U.S. Pat. No. 4,822,373 to Olson discloses a method of imparting stain resistance to nylon fiber that includes applying a mixture of a partially sulfonated novolac resin and a polymethacrylic acid.
European Patent Application No. 88311826.7 filed by E. I. Du Pont Nemours and Company describes stain resistant polyamide fibers prepared by treating the fiber with a hydrolyzed ethylenically unsaturated aromatic maleic anhydride polymer in combination with a sulfonated aromatic condensation polymer.
Although polyamide fibers treated with sulfonated condensation polymers have improved resistance to staining by acid dyes, the resistance is reduced or eliminated after several shampooings, because the sulfonated aromatic condensation polymers are stripped from the fiber. Regardless of the effectiveness of a sulfonated material in imparting stain resistance to polyamides, after several shampooings, the polyamide is just as susceptible to staining as before treatment. This is particularly disadvantageous in a commercial or industrial setting, because of the need for frequent cleaning.
Not only are polyamide fibers easily stained by anionic materials, they are also soiled easily. Fluorochemicals are typically used to reduce the tendency of soil to adhere to the fiber surface, and reduce fiber wettability. Fluorochemicals also provide a physical barrier to the staining material. Examples of commercially available fluorochemical coatings include Scotchgard� 358 and 352 (Minnesota Mining & Mfg. Co.) and Zepel� and Teflon� (E. I. Du Pont Nemours & Co.). Antron Plus� carpet manufactured by Du Pont contains nylon carpet fibers coated with fluorocarbons. However, fluorochemical coatings alone provide no resistance to staining by acid dyes.
There is a need for a convenient method to impart permanent stain resistance to polyamide fibers that is appropriate for industrial use.
Therefore, it is an object of the present invention to provide a method to impart stain resistance to natural or synthetic polyamide fibers that will not be removed on washing the fiber.
It is another object of the present invention to provide a method for treating natural or synthetic polyamide fiber that is mild enough not to damage other materials attached to the fiber.
It is still another object of the present invention to provide a method to impart permanent stain resistance to nylon carpet and carpet tile for commercial or industrial use.
It is yet another object of the present invention to provide a method to impart permanent stain resistance to natural or synthetic polyamide fabric.
It is a further object of the present invention to provide nylon carpet tile that is permanently stain resistant.
The present invention is a method to impart permanent stain resistance to polyamide fibers that includes treating the fiber with an isocyanate under moderate conditions that do not damage other materials that the fiber is attached to. The invention provides nylon carpet and carpet tile that are highly suited for commercial use because they retain their stain resistance after repeated washings.
According to the invention, the terminal amine group of the polyamide fiber is reacted with a monoisocyanate, a diisocyanate, a polyisocyanate, or an oligomer or polymer containing isocyanate functional groups, or a combination of these, to produce a terminal substituted urea. The fiber can be treated before or after manufacture into an article such as fabric, carpet, or carpet tile. The fiber can be coated with a fluorocarbon after or during isocyanate treatment.
Treatment of polyamide fiber with an isocyanate provides a stain resistance that is significantly better than that provided by sulfonated aromatic condensation products now marketed for this purpose, because the protection provided by isocyanate treatment is permanent. The treatment is effective after extensive washings and even after extraction with hot ethanol. By comparison, the present stain resist treatments for nylon fibers are stripped from the fiber after repeated washing or extraction with ethanol.
Samples of nylon 6 fiber treated with isocyanate resist staining after being soaked overnight in cherry Kool Aid� at room temperature, or after heating the fiber in cherry Kool Aid� at 100� C. for two hours. In comparison, untreated nylon fiber resists staining by cherry Kool Aid� at room temperature for approximately five minutes.
The isocyanate can be effectively applied to any synthetic or natural fiber having terminal amine groups using a wide variety of means. In the preferred method, the fiber or fibrous article is treated with a foam or spray of isocyanate, and then passed through a heating unit. In another embodiment, the fiber or fibrous article is soaked in the isocyanate and then heated until dry. Alternatively, the isocyanate can be applied by pad squeeze or kiss roll. The length of time and temperature needed to dry the fiber or article will vary depending on the type of oven and the solvent system used to apply the isocyanate. A drying temperature should be chosen that does not damage the fiber or any materials in the fibrous article.
FIG. 1 is an illustration of the chemical structures of a,a-dimethyl meta-isopropenyl benzyl isocyanate (TMI), 4,4'-diphenylmethane diisocyanate (MDI), and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI, also called isophorone diisocyanate).
Isocyanates can be used to impart permanent stain resistance to any fiber that has reactive terminal amino groups, for example, polyamides. As used below, the term polyamide includes homopolymers or copolymers that contain polyamide linkages. Polyamides are found in a wide variety of fibers and fabrics, such as wool, silk, natural leather, synthetic leather and nylon.
Nylon is a synthetic polyamide prepared by the polycondensation of a dicarboxylic acid and a diamine, such as adipic acid and hexamethylene diamine (nylon 6,6), or from a diisocyanate and a dicarboxylic acid. In manufacturing nylon from a diamine and a dicarboxylic acid, an excess of diamine can be used to produce a fiber that has two terminal amine groups instead of a terminal amine and a terminal carboxylic acid. An excess of amine is typically used to increase the acid dyeability of the fiber. This process, however, can also increase the tendency of the fiber to stain. Nylon can also be produced from a cyclic amide such as caprolactam (nylon 6).
As used herein, the term "isocyanate" refers to any compound that has at least one isocyanate functional group, including but not limited to monoisocyanates, diisocyanates, polyisocyanates, and polymers containing isocyanate functional groups.
Polyamides are known to react with isocyanates to form substituted ureas, and have been so reacted in the past to alter properties other than stain resistance. Kondo, et al., The Chemical Society of Japan 9, 1459 (1984) report that the surface of a nylon film can be made soil (water and oil) resistant by refluxing it for fourteen hours with p-(perfluorononyl)phenyl isocyanate. The length of treatment is unsuitable for an industrial procedure and can result in undesirable side reactions if any other material is attached to the fiber. U.S. Pat. 4,672,094 discloses that a polyamide can be reacted with an organic diisocyanate to increase the molecular weight of a polyamide prepared from a diisocyanate and a dicarboxylic acid. Tenchev, K. H., et al., Mater. Plast. (Bucharest) 18(2), 108-112 (1981) describes the modification of polyamide tire cord with isocyanates to alter the relative elongation, tensile strength, and crystallinity of the cord. Nikolaev, V. N., et al., Viniti 3373-77 (1977) discloses that the modification of polyamide fabric with a diisocyanate improves thermostability and adhesion properties. German Patent Application DE 3526272 discloses that modification of polyamides with monoisocyanates increases fold capability, mold release behavior and notch impact strength. Japanese Patent Application 60-93065 describes polyamide resins suitable for use as insulator materials such as wire coatings prepared by reacting 0.5-2.0 isocyanate radicals for each amide moiety in the polyamide chain. None of these references provide a method to increase the stain resistance of polyamide fibers
In one embodiment, the disclosed invention is a method to impart permanent stain resistance to polyamide fibers that includes treating the fiber with a monoisocyanate that covalently binds to the terminal amine group of the polyamide to form a terminal substituted urea, according to the following equation: ##STR1## wherein
R is any hydrocarbon or substituted hydrocarbon in an isocyanate that is capable of forming a stable bond with the terminal amine and that does not participate in undesirable side reactions; and R' the polyamide chain that terminates with the reactive amine. The fiber can be treated with a homogeneous solution of monoisocyanate, or with a mixture of isocyanates.
R is defined functionally to emphasize that the invention is not restricted to the use of a certain family of monoisocyanates, but rather, lies in the permanent "capping" of the terminal amine of the polyamide with any suitable isocyanate.
The choice of isocyanate will determine in part how the fiber is treated; for example, whether the isocyanate can be applied in an aqueous solution, an emulsion, or in an organic solvent. The choice of isocyanate will also determine the treatment conditions. For example, aliphatic isocyanates react with terminal amines more slowly than aromatic isocyanates, and therefore may require more vigorous application conditions. Further, it has been discovered that aliphatic isocyanates have less tendency to yellow than aromatic isocyantes after incorporation into the fiber. Aromatic isocyanates, however, tend to provide superior stain resistance.
Preferably, R is an aromatic, heterocyclic, aliphatic, araliphatic, alkaryl, or cycloaliphatic group of C1 to C24, optionally with hetero (O,S, or N) or CONH linkages, and optionally substituted with chlorine, bromine, or fluorine. The term aliphatic includes alkanes, alkenes, and alkynes.
Examples of suitable monoisocyanates include a,a-dimethyl meta-isopropenyl benzyl isocyanate (TMI, available from American Cyanamid Company, see FIG. 1), phenyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, hexyl isocyanate, 2-ethylhexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethyl isocyanate, decyl isocyanate, 2-norbornyl-methyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate (stearic isocyanate), oleic isocyanate, 3-butoxypropyl isocyanate, toluyl isocyanate, chlorophenyl isocyanate, dichlorophenyl isocyanate, benzyl isocyanate, and 1-naphthyl isocyanate.
The monoisocyanates can be purchased commercially or can be synthesized by methods known to those skilled in the art, for example, by the reaction of phosgene with the desired amine.
Isocyanates do not react appreciably with the amide linkages of the polyamide fibers under the conditions described here to treat the fiber, because the amide nitrogen is significantly less reactive than the nitrogen in the terminal amine groups.
In a preferred embodiment, the isocyanate that is reacted with the polyamide fiber has a sufficiently low molecular weight that it penetrates to some extent into the fiber before reaction. Monomers and oligomers of up to ten monomers can typically penetrate the fiber with ease. The optimal molecular weight of the isocyanate will depend on the porosity and nature of the fiber. The optimal isocyanate treatment provides a dense protective layer at and closely below the surface.
In an alternative embodiment, terminal amine groups of a polyamide fiber can be permanently linked by reaction with a diisocyanate according to the equation: ##STR2## wherein
R" is any hydrocarbon or substituted hydrocarbon in a diisocyanate that is capable of forming stable bonds with the terminal amine and that does not participate in undesirable side reactions; and R' is the polyamide chain that terminates with the reactive amine.
As above, R" is defined functionally to emphasize that the invention is not restricted to a certain family of diisocyanates, but instead covers within its scope the use of any diisocyanate that will crosslink with the terminal amine groups to form permanent bonds that protect the fiber from acid dyes.
Preferably, R" an aromatic, heterocyclic, aliphatic, araliphatic, alkaryl, or cycloaliphatic group of C1 to C24, optionally with hetero (O,S, or N) or CONH linkages, and optionally substituted with chlorine, bromine, or fluorine.
Examples of suitable diisocyanates include 4,4'-diphenylmethane diisocyanate (MDI, available from ICI Polyurethanes Group, West Deptford, New Jersey, see FIG. 1); PBA 2259 (a more stable water dispersible version of MDI also available from ICI Polyurethanes Group); 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI, or isophorone diisocyanate, available from Huls America, Inc., see FIG. 1); toluene diisocyanate (TDI); hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, cyclohexyl diisocyanate, methylenebis-(4-cyclohexylisocyanate), phenylene diisocyanate, diphenylether-4,4'-diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, polyether diisocyanate, polyester diisocyanate, polyamide diisocyanate, and dimer acid diisocyanate (a diisocyanate prepared from the reaction product of two unsaturated carboxylic acids).
The use of multifunctional isocyanates, such as triisocyanates and tetraisocyanates to impart stain resistance to nylon fibers is also considered within the scope of this invention.
The stain resistance of a polyamide fiber can also be enhanced by reaction with a polymer that has isocyanate functional groups. Suitable polymers include those with aromatic or aliphatic backbones, for example, Desmodour E-14 from Mobay Corporation.
Isocyanate functionalized polymers also provide a protective coating for the polyamide fiber. If the functionalized polymer is water repellent, for example, if it is halogenated, it will decrease the tendency of soil or liquid to adhere to the fiber surface. A water soluble isocyanate can be prepared by reacting a diisocyanate with a perfluorinated alcohol. An example is the reaction of MDI with 1/2 of an equivalent of perfluorononyl alcohol. Alternatively, a polymer can be selected that imparts anti-static qualities.
The isocyanate can be reacted with the polyamide fiber in a blocked or masked form, or in a mixture that includes unblocked and blocked derivatives. Methods for blocking isocyanates are described in U.S. Pat. No. 4,530,859, incorporated herein by reference; Doyle, "The Development and Use of Polyurethane Products," McGraw-Hill (1971); and Saunders and Frisch, "Polyurethanes: Chemistry and Technology," Part II, Interscience (New York 1964), pages 8-49.
Typical blocking agents include phenol type blocking agents, including phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, hydroxybenzoic acid esters, and 2,5-di-tert-butyl-4-hydroxytoluene;
lactam type blocking agents, including ε-caprolactam, δ-valerolactam, butyrolactam, and β-propiolactam;
active methylene type blocking agents, including diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, and t-butylacetoacetate;
alcohol type blocking agents, including hexane diol, ethylene glycol, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monoether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic acid esters, lactic acid, lactic acid esters, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, and acetocyanohydrin;
mercaptan type blocking agents, including butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, and ethylthiophenol;
acid amide type blocking groups, including acetoanilide, acetoacetanisidide, acetotoluide, acrylamide, methacrylamide, acetamide, stearylamide, and benzamide;
imide type blocking agents, including succinimide, phthalimide, and maleimide;
amine type blocking agents, including diphenyl amide, phenolnaphthyl amide, zylidine, N-phenylzylidine, carbazole, aniline, naphthyl amide, butyl amine, dibutyl amine, and butylphenyl amide;
imidazole type blocking agents, including imidazole, and 2-ethylimidazole;
urea type blocking agents, including urea, thiourea, ethylene urea, ethylene thiourea, and 1,3-diphenylurea;
carbamate type blocking agents, including phenyl N-phenylcarbamate, and 2-oxazolidone;
imine type blocking agents, including ethyleneimine;
oxime type blocking agents, including formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, dioctyl monoxime, benzophenone oxime, and cyclohexanone oxime; and
sulfite type blocking agents, including sodium bisulfite and potassium bisulfite.
For example, the reaction of an alcohol with an isocyanate produces a urethane. This reaction is reversible. Heat forces the equilibrium back toward formation of the isocyanate. When the temperature rises above 100� C., the water in the solution is evaporated, and the isocyanate is forced to react with the polyamide terminal amine, which is easily reversible, or the alcohol, which again is a reversible reaction.
It is important to choose a blocked isocyanate that generates a free isocyanate at a temperature below which the fiber or fibrous article to be treated is damaged. The suitability of a desired blocked isocyanate can be determined easily by a small scale trial run carried out according to procedures described in Section V.
Molecules that are capable of thermal rearrangement to isocyanates are also suitable to impart stain resistance to polyamides. For example, U.S. Pat. Nos. 4,109,599 and 4,410,689, incorporated herein by reference, disclose bis-cyclic ureas that rearrange to aliphatic diisocyanates.
Oligomers of aromatic diisocyanates can be prepared by reacting an excess of diisocyanate with a diol such as hexane diol or ethylene glycol to form a urethane. This urethane can be used as a precursor to the diisocyanate in polyamide fiber treatment. The urethane can be prepared in advance or formed in situ. It is preferred to have the ratio of diol to diisocyanate below 1:1 so that an oligomer is formed with terminal isocyanate groups, and not terminal hydroxyl groups. The most preferred range is 0.3 or less diol to isocyanate. The diol can be fluorinated or optionally substituted with groups that do not interfere with the isocyanate reaction.
Aliphatic isocyanates typically react slowly with blocking agents, and will only form useful oligomers in situ with the use of catalysts.
The desired isocyanate can be effectively applied to any synthetic or natural polyamide fiber using a wide variety of means, for example, in a batch system, a pad squeeze or a kiss roll coating. The isocyanate can also be effectively applied as a foam or in a spray. Alternatively, the isocyanate can be applied by dipping the fiber into an isocyanate solution.
In the preferred method to impart superior and permanent resistance to common staining materials such as FD&C No. 40 (the staining component of cherry Kool Aid�), wine, and mustard with tumeric, the polyamide fiber is treated with an isocyanate before it is dyed or manufactured into fabric or carpet. This procedure allows for thorough treatment of the fiber and avoids the problem of interfering additives or coatings applied during manufacture. However, after the fiber has been treated with an isocyanate, it will not be susceptible to further treatment that involves the formation of ionic or covalent bonds with the terminal amine groups on the polyamide fiber, including coloring of the fiber with anionic materials. The stain resistant fiber can be colored or otherwise treated with compounds that bind to the carboxylic acid end groups of the polyamide fiber.
Alternatively, the polyamide fiber can be treated with the isocyanate after it has been manufactured into an article such as carpet or carpet tile. The treatment must be mild enough not to damage any of the materials in the article, including backing materials and adhesives. For example, bitumen backed carpet must be treated at a lower temperature than polyvinyl chloride backed carpet.
The isocyanate is applied in a solution of any suitable concentration, typically between 0.5% to 60% by weight. The preferred weight percent of isocyanate applied to the polyamide, based on the weight of the fiber ranges from 0.5 to 5%, and more typically from approximately 1 to 2%. Isocyanate foams can be applied with very high concentrations of isocyanate. A preferred concentration range for pad squeeze or kiss roll applications is between 0.05 and 100 grams/liter. A more preferred concentration is between 5 and 50 grams/liter. The optimal concentration (in grams/liter) will depend on the molecular weight of the isocyanate. If the isocyanate solution is too dilute, the isocyanate may be applied unevenly. A large wet pick-up (20-300%) is desireable to provide uniform isocyanate treatment.
It is very important that the polyamide fibers be very dry when treated with the isocyanate. Even damp fiber will not react suitably with the isocyanate to provide adequate stain resistance. The isocyanate should be reacted with the fiber for the minimum time period and at the lowest temperature that is effective to complete the reaction. The time and temperature of reaction will depend in part on the reactivity of the isocyanate, and can be determined without undue experimentation. The time of reaction typically ranges from one to sixty minutes. The length of time required for reaction is a function of the intensity and temperature of the heating unit used. A time period of from one to ten minutes is usually sufficient for isocyanate/polyamide reactions in ovens that reach 120� C. or higher. A time and temperature should be selected that allows the isocyanate to react with the terminal amine groups of the polyamide without undesired reaction of the isocyanate with the internal amide linkages of the polyamide. Appropriate temperatures for reaction typically range from 140� F. to 400� F. (60� C. to 205� C.). The carpet and fabric fiber typically should not reach over approximately 140� C. when placed in a heating unit with an air temperature of between 60� C. to 205� C. for the appropriate time period. Aromatic isocyanates in general react faster and under milder conditions than aliphatic isocyanates.
The isocyanate treated fiber can be heated with a wide variety of known means, including conventional ovens, forced air ovens, microwave and infared heaters. When using an isocyanate that reacts slowly with the fiber, or when carrying out the reaction in the absence of a catalyst, it is sometimes desirable to include a post-cure step in which the heat is continued until a low percentage of moisture is achieved.
Catalysts can be used to facilitate the reaction of the isocyanate with the polyamide. Suitable catalysts include organic tertiary amines such as 1,4-diazabicyclo[2.2.2]octane (DABCO), or metallic catalysts such as tin, antimony or other heavy metal compounds.
Typically, the dry fiber is first soaked with the isocyanate solution until saturated, and then the fiber is heated to initiate reaction. It is preferred to heat the fiber to dryness. The length of time and temperature needed to complete the reaction will vary depending on the type of oven used and the air circulation in the oven.
As an example, a nylon yarn can be soaked in an isocyanate solution and heated at 120� C. for 10-15 minutes to impart permanent stain resistance. If desired, the yarn can be washed after treatment to remove excess reactants.
In another example, the isocyanate can be foamed or sprayed onto carpet fiber, and then heated in an oven that is at a temperature ranging from 120� C. to 205� C. for one to ten minutes, typically two to five minutes.
The treatment is very conveniently carried out in an organic such as toluene, tetrachloroethane, tetrahydrofuran, or dimethylformamide. However, due to environmental concerns, it is often desireable to treat the fiber in an aqueous system. If the isocyanate is not water soluble, it can be mixed with a small amount of organic cosolvent such as cyclohexane or dimethylformamide that is then mixed with water. Alternatively, the isocyanate can be applied in an emulsion prepared by methods well known to those of skill in the art. The surfactant used in the emulsion should not contain active hydrogens that will react with the isocyanate. Examples of suitable surfactants include sodium dodecylbenzene sulfonate, and sodium dioctyl sulfosuccinate. Further, certain isocyanates can be made water dispersible by adding hydrophilic groups that do not contain active hydrogens. An example of a water dispersible isocyanate is PBA 2259 from ICI Americas, Inc. MDI can also be purchased in a water dispersible form from the same company.
The present invention can be used to impart permanent stain resistance to all types of nylon fibers, including nylon 6; nylon 6,6; nylon 10,11,12; and copolymer structures that have amino end groups.
As characterized below, the method for treating polyamides with isocyanates to impart stain resistance is applicable to a wide variety of isocyanates and final products.
Nylon 6 yarn (0.3 g) was dipped into a 1% wt/wt solution of methylenediphenyl diisocyanate (MDI) in toluene for 10 seconds. The yarn was removed and the excess solution allowed to drain off, resulting in a wet pick-up of 158%. The yarn was heated in an oven at 120� C. for 1 hour.
A three inch square of carpet tile was placed upside down in a pan containing a 1% wt/wt solution of MDI in toluene. The height of the solution in the pan was sufficient to submerge the tile yarn but not contact the tile backing. The tile was removed from the solution after soaking for 10 seconds, which resulted in a 205% wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120� C. for 1 hour.
A three inch square of carpet tile was placed upside down in a pan containing a 2% wt/wt solution of a,a-dimethyl meta-isopropenyl benzyl isocyanate (TMI) in toluene. The height of the solution in the pan was sufficient to submerge the tile yarn but not contact the tile backing. The tile was removed from the solution after soaking for 10 seconds, which resulted in a 220% wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120� C. for 1 hour.
An emulsion of 2% isophorone diisocyanate (IPDI) is prepared by dissolving 0.5 parts by weight of sodium dodecylbenzene sulfonate in 97.5 parts of water and adding 2 parts of IPDI with continuous stirring. Hexane diol (0.4 parts) is then added to the emulsion. The emulsion is applied to the carpet tile by kiss-roll or pad squeeze. After the excess solution is allowed to drain off, the carpet tile is heated in an oven of forced air at 116� C. for 6-7 minutes.
A three inch square of carpet tile was placed upside down in a pan containing an emulsion of 2% isophorone diisocyanate (IPDI) made by dissolving 0.5 g of sodium dodecylbenzene sulfonate in 97.5 g of water and adding 2 g of IPDI with continuous stirring. The height of the solution in the pan was sufficient to submerge most of the tile yarn but not contact the tile backing. The tile was removed from the solution after soaking for 10 seconds, which resulted in a 250% wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120� C. for 1 hour.
A three inch square of carpet tile was placed upside down in a pan containing a 2% wt/wt solution of PBA 2259 in water. The height of the solution in the pan was sufficient to submerge the tile yarn but not contact the tile backing. The tile was removed from the solution after soaking for 10 seconds, and excess solution drained, resulting in a 140% wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120� C. for 1 hour.
An emulsion of 2% IPDI is prepared by dissolving 0.5 grams of sodium dodecylbenzene sulfonate in 97.5 grams of water and then adding 2.0 grams of IPDI with continuous stirring. Ethylene glycol (0.4 grams) is then added to this mixture. Nylon 6 yarn (0.3 g) is dipped into the solution for 10 seconds and then removed. The excess solution was then allowed to drain off. The yarn was heated in an oven at 120� C. for 1 hour.
An emulsion of 2% IPDI was made by dissolving 0.25 grams of sodium dodecylbenzene sulfonate in 97.75 grams of water and then adding 2.0 grams of IPDI with continuous stirring. Hexane diol (0.4 grams) was then added to this mixture. A three inch square of carpet tile was placed upside down in a pan containing this emulsion for approximately ten seconds. The height of the solution in the pan was sufficient to submerge most of the tile yarn but not contact the tile backing. The carpet tile sample was then removed, and the excess solution drained off. This procedure resulted in a 240% pick-up. The tile was then heated in an oven for one hour.
After the carpet tile has been assembled and printed, it is passed through an atmospheric steam oven for about eight minutes and then the excess water is vacuumed off. A solution of 2% PBA 2259 in water is then applied to the fiber by kiss roll or pad squeeze. The tile is then heated in a forced air oven at 116� C. for 6-7 minutes.
After the carpet tile has been assembled, and after overprinting if desired, the nylon fibers are vacuum dried and then sprayed with a solution of 2% IPDI to a wet pick up of 200-250%, and then heated at 240� C. for 6-7 minutes, or until the fibers are completely dry.
A foam is prepared by whipping a solution of 25 grams of PBA 2259 and 3 grams of sodium dodecylbenzene sulfonate in 72 grams of water. The foam is mechanically worked into the fibers, and then the tile is dried at 120� C.
The stain resistance of isocyanate treated nylon fiber was tested by soaking light gray nylon 6 carpet tiles treated as in Examples 2, 5, and 6, together with an untreated tile, for 24 hours in a cherry Kool-Aid� solution (unsweetened) prepared according to the directions on the package. The samples were rinsed with water for about 10 seconds after soaking and then the extent of staining was determined. The results are provided in Table 1.
TABLE 1______________________________________Stain Resistance of Isocyanate Treated Nylon CarpetTilesSample Staining______________________________________Untreated carpet Bright redCarpet Tile of Example 2 No stainCarpet Tile of Example 5 Light pink tintCarpet Tile of Example 6 No stainCarpet Tile of Example 8 Very light pink tint______________________________________
As indicated in Table 1, treatment with methylene diphenyl diisocyanate (Examples 2 and 6) provides excellent protection to nylon fiber against staining by acid dyes. Isophorone diisocyanate (Example 5) as well as a mixture of Isophorone diisocyanate and hexane diol (Example 8) also provides superior protection against acid dyes. The data in Table 1 illustrates the general observation that aromatic isocyanates typically provide better stain resist treatment to nylon fibers than aliphatic isocyanates.
Nylon carpet tile samples prepared as described in Examples 2, 5, and 7, as well as a sample of residential shag Cabin Craft carpet (style A3-55 Comfort) treated with Du Pont's Stainmaster� formulation (a sulfonated formaldehyde condensation polymer in combination with a fluorocarbon coating), a sample of light gray nylon carpet tile treated with a sulfonated aromatic condensation polymer (SAC, purchased from Grifftex Inc.) alone, and a sample of carpet treated with BASF Scotchgard� (a fluorochemical treatment) were washed five times under identical conditions using a 1% aqueous solution of AATCC standard detergent #124 with a typical residential washing machine. The samples were then soaked for 24 hours in cherry Kool Aid�, rinsed with water, and then analyzed for extent of staining. The results are provided in Table 2.
TABLE 2______________________________________Comparison of Permanence of Stain Resist TreatmentsSample Staining______________________________________Before WashingSAC Treated No stainFrom Examples 2 and 7 No stainFrom Example 5 Light pink tintStainMaster � (Du Pont) No stainBASF Scotchgard � RedAfter WashingSAC Treated Bright redFrom Examples 2 and 7 Almost undetectableFrom Example 5 Light pink tintStainMaster � (Du Pont) PinkBASF Scotchgard � Bright red______________________________________
As indicated in Table 2, carpet tile samples treated as described in Examples 2, 5, and 7 retain their stain resistance after five washings. The SAC treated nylon carpet sample completely lost its stain resistance after five washings. The StainMaster� treated sample lost significant stain resistance after washing, however, the fluorochemical coating appeared to prolong the effectiveness of the treatment. The fluorochemical coating would have the same effect on isocyanate treated polyamide fibers. Further, as indicated above, the fluorochemical coating alone (Scotchgard) provides no protection from staining.
Polymeric fibers with terminal amine groups can be made permanently stain resistant by reacting the polymer with a carboxylic acid or its derivative that covalently binds with the amine. Examples of suitable carboxylic acid derivatives include acid chlorides, acid anhydrides, and esters. Acid chlorides are generally less preferred than isocyanates because they have a very strong odor and are highly reactive in water. The by-product of the reaction of an acid chloride with water is hydrochloric acid. Therefore, when using an aromatic acid chloride in an aqueous system, a base should be added to neutralize the acid generated.
Alternatively, the terminal amine can be reacted with a sulfonyl chloride, sulfonyl amide, sulfonyl isocyanate, or acyl isocyanate. Sulfonyl isocyanates and acyl isocyanate are preferably applied in an organic solvent because they are typically too reactive to be used in an aqueous system.
Two percent wt/wt solutions of benzoyl chloride in toluene and water (containing 1% sodium bicarbonate) were prepared. Nylon 6 carpet tile samples were separately soaked at room temperature for about two minutes in the two solutions (wet pick-up 150% and 250%, respectively) and then dried at 120� C. The samples were then placed in cherry Kool-Aid� for two hours and rinsed. The solvent treated sample had only a very slight staining, whereas the aqueous treated sample had only moderate staining. The control was intensely stained.
Two percent solutions of succinic anhydride (SA) and phthalic anhydride (PA) in dimethylformamide (DMF) were prepared. Two percent emulsions of each were also prepared using a small amount of DMF (4% wt/wt for SA and 6% wt/wt for PA) and 0.3% wt/wt of Siponate DS-10 (sodium dodecylbenzene sulfonate, purchased from Alcolac, Inc., Baltimore, Md.) in water. Nylon 6 carpet tile samples were separately soaked in these solutions and then dried for about one hour at 120� C. The samples, along with a control and a sample of carpet treated with a,a-dimethyl meta-isopropenyl benzyl isocyanate (TMI) were then soaked in cherry Kool-Aid� for 24 hours and allowed to dry. The results are provided in Table 3. As indicated, the isocyanate (TMI) provides better resistance to acid dyes than the anhydrides in aqueous systems, however, the reverse is true in solvent systems.
TABLE 3______________________________________Stain Resistance of Nylon Fibers Treated with AcidAnhydrides______________________________________ Water DMF TMI SA PA DS-10______________________________________Sample 1 94 g 4 g 2 g -- -- 0.3 gSample 2 98 g -- 2 g -- -- 0.3 gSample 3 94 g 4 g -- 2 g -- 0.3 gSample 4 92 g 6 g -- -- 2 g 0.3 gSample 5 -- 98 g -- 2 g -- --Sample 6 -- 98 g -- -- 2 g --______________________________________Sample Staining______________________________________1 Slight2 Slight (but better than sample 1)3 Slight - moderate4 Moderate (PA didn't emulsify well)5 Very slight6 Very slightControl Intense______________________________________
The stain resisting performance of polyamide fibers treated with an isocyanate can be improved by applying a fluorochemical coating to the treated fiber. Examples of suitable fluorochemical coatings include Scotchgard� 358 and 352 (Minnesota Mining & Mfg. Co.); Zepel� and Teflon� Toughcoat (E. I. Du Pont Nemours & Co.); Milease F-86, manufactured by ICI Americas, Inc.; Aurapel FC-340 and 342, manufactured by Auralux Corporation; NK Guard FG280, manufactured by NICCA Chemicals; and Glo-Guard CFC, manufactured by Glo-Tex Chemicals.
The amount of fluorochemical required to provide a coating that cannot be penetrated by water will vary depending on the particular fluorochemical used. Methods for applying fluorochemical coatings are known to those skilled in the art, and are described in a number of patents, including U.S. Pat. No. 4,619,853 to Blythe, U.S. Pat. No. 4,388,372 to Champameria, U.S. Pat. No. 4,839,212 to Blythe, et al., and U.S. Pat. No. 4,680,212 to Blythe, et al., all of which are incorporated herein by reference.
If desired, an antimicrobial compound or combination of compounds can be added to the fluorochemical coating. Examples of antimicrobial compounds that can be included in the coating include OBPA (10,10'-oxybisphenarsine), marketed under the name Vinyzene BP-505 DOP by Morton Thiokol, Inc.; silicone quaternary ammonium salts such as Sylgard, manufactured by Dow Corning Corporation; and monoesters of phosphoric acid or its salt, preferably the di(2-hydroxyethyl)cocoamine salt of 2-ethylhexylphosphoric acid, as described in U.S. Ser. No. 07/047,561, filed Apr. 27, 1987, entitled "Microbiocidal Composition and Method of Preparation Thereof," now U.S. Pat. No. 4,935,232, and incorporated herein by reference.
The fluorochemical used to coat the stain treated fibers can also be mixed with other polymers or monomers to increase its effectiveness, including polymethylmethacrylate.
Modifications and variations of the present invention of permanent stain resistant treatment for polyamide fibers will be obvious to those of skill in the art from the foregoing detailed description of the invention. Such modifications and variations are intended to come within the scope of the appended claims.
|Cited Patent
|Filing date
|Publication date
|12 May 1967
|15 Oct 1968
|Agriculture Usa
|Fibrous material having a polyamide bound thereto by a polyfunctional fixative
|11 Dec 1978
|26 Feb 1980
|The Upjohn Company
|Amide-containing diisocyanates and preparation thereof
|16 Dec 1977
|25 Mar 1980
|Allied Chemical Corporation
|Fluorinated polyalkylene polyamides as stain repellents
|16 Jun 1982
|18 Oct 1983
|The Upjohn Company
|Preparation of polyurethane from bis(cyclic urea) and polymeric polyol
|3 Oct 1983
|26 Mar 1985
|Monsanto Company
|Antisoiling nylon carpet yarns
|15 Nov 1982
|23 Jul 1985
|Minnesota Mining And Manufacturing Company
|Method of preparing a polymeric coating composition from a blocked isocyanate-functional polymeric compound and a crosslinking agent which is insoluble in aprotic solvents
|21 Jan 1986
|9 Jun 1987
|The Dow Chemical Company
|Method for increasing the molecular weight of polyamides and polyesteramides
|21 Jun 1989
|9 Jan 1990
|Monsanto Company
|Process for dyeing stain resistant nylon carpets
|17 Jun 1988
|10 Jul 1990
|Bayer Aktiengesellschaft
|Textile sheet-like structure with reactive resin
|4 May 1985
|6 Nov 1986
|Bayer Ag
|Mit monoisocyanaten modifizierte polyamide
|27 Jul 1989
|31 Jan 1990
|Wool Research Organisation Of New Zealand Inc.
|A stain blocking system
|Title not available
|Title not available
|Kondo, et al., The Chemical Society of Japan, 9, 1459 (1984).
|Nikolayev, et al., Viniti, 3373 77 (1977).
|Nikolayev, et al., Viniti, 3373-77 (1977).
|Tenchev, et al., Mater. Plast. (Bucharest) 18(2), 108 112 (1981).
|Tenchev, et al., Mater. Plast. (Bucharest) 18(2), 108-112 (1981).
|Citing Patent
|Filing date
|Publication date
|26 Aug 1993
|10 Jan 1995
|Textilma Ag
|Method and apparatus for coating flat textile bodies, especially carpet panels
|2 Jan 2002
|2 Nov 2004
|Dupont Textiles & Interiors, Inc.
|Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby
|2 Jan 2002
|8 Feb 2005
|Invista North America S.A.R.L.
|Method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
|31 Jul 2002
|27 Feb 2007
|Milliken & Company
|Flooring system and method
|8 Dec 2004
|2 Oct 2007
|Shaw Industries Group, Inc.
|Methods of treating and cleaning fibers, carpet yarns and carpets
|20 Sep 2004
|12 Feb 2008
|Trichromatic Carpet Inc.
|Enhancement of durable soil release and soil resist, stain resist water and oil repellency and the softness of fibrous substrates, the substrates so treated and the treating composition
|21 Aug 2007
|10 Feb 2009
|Columbia Insurance Company
|Methods of treating and cleaning fibers, carpet yarns and carpets
|20 Dec 2005
|9 Mar 2010
|Fujifilm Corporation
|Functional group-introduced polyamide solid phase
|24 Jan 2005
|31 Aug 2010
|Columbia Insurance Co.
|Methods and compositions for imparting stain resistance to nylon materials
|3 Feb 2003
|16 Nov 2010
|Casematic, S.A. De C.V.
|Polymer based sausage casing
|27 Oct 2003
|22 Mar 2011
|Honeywell International Inc.
|Planarization films for advanced microelectronic applications and devices and methods of production thereof
|19 Dec 2007
|29 Mar 2011
|E.I. Dupont De Nemours And Company
|Cyclic olefin-maleic acid copolymers for stain resists
|6 Nov 2007
|11 Sep 2012
|E.I. Du Pont De Nemours And Company
|Reduction or prevention of dye bleeding
|16 Oct 2012
|17 Feb 2015
|Huntsman International Llc
|Method of increasing chlorine fastness
|16 Nov 2001
|19 Sep 2002
|Higgins Kenneth B.
|Textile product and method
|2 Jan 2002
|10 Oct 2002
|Markus Baumann
|Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby
|2 Jan 2002
|17 Oct 2002
|Markus Baumann
|Method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
|15 Dec 2003
|1 Jul 2004
|Markus Baumann
|Method of imparting stain resistance
|15 Dec 2003
|1 Jul 2004
|Markus Baumann
|Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby
|24 Jul 2003
|27 Jan 2005
|Shaw Industries Group, Inc.
|Methods of treating and cleaning fibers, carpet yarns and carpets
|8 Oct 2004
|15 Sep 2005
|Dupont Textiles & Interiors, Inc.
|Method of after-treatment of dyeable nylon textile surface with a stain resist and the article produced thereby
|14 Jul 2004
|19 Jan 2006
|Daike Wang
|Conditioning method for improving polyamide cleanability and polyamides so conditioned
|10 Aug 2005
|16 Feb 2006
|Formosa Taffeta Co., Ltd.
|Yarns and fabrics having long-lasting mosquito repellent or antibacterial effect and their preparation
|20 Sep 2004
|23 Mar 2006
|Yassin Elgarhy
|Enhancement of durable soil release and soil resist, stain resist water and oil repellency and the softness of fibrous substrates, the substrates so treated and the treating composition
|20 Dec 2005
|22 Jun 2006
|Fuji Photo Film Co., Ltd.
|Functional group-introduced polyamide solid phase
|2 Sep 2005
|8 Mar 2007
|Materniak Joyce M
|Reduction of turmeric and iodine staining
|3 Jul 2000
|9 Jan 2002
|E.I. Du Pont De Nemours And Company
|Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby
|11 Aug 2005
|15 Feb 2006
|Formosa Taffeta Co.,Ltd.
|Yarns and fabrics having long-lasting mosquito repellent or antibacterial effect and their preparation
|7 Jul 2000
|18 Jan 2001
|Baumann Markus
|A method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
|16 Oct 2012
|16 May 2013
|Huntsman Advanced Materials (Switzerland) Gmbh
|Method of increasing chlorine fastness
|U.S. Classification
|428/96, 427/393.4, 8/115.67, 428/423.5
|International Classification
|Cooperative Classification
|European Classification
|5 Apr 1991
Owner name: INTERFACE, INC. A CORP. OF GEORGIA, GEORGIA
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|8 May 2001
|Maintenance fee reminder mailed
|9 Jan 2004
Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION,GEORGIA
Free format text: SECURITY INTEREST;ASSIGNOR:INTERFACE, INC.;REEL/FRAME:014910/0414
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Owner name: U.S. BANK NATIONAL ASSOCIATION,GEORGIA
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Effective date: 20090605


text:
Open Badges Research article
Validation of a Persian version of the OIDP index
BMC Oral Health 2007, 7:2 doi:10.1186/1472-6831-7-2
Clinical Criterion Validity
JAVIER MONTERO (2007-09-17 12:08) University of Salamanca, Spain
It is a good study to reach the transcultural validation of the OIDP. Is there any relevant clinical criteria scoring the OIDP? What about gender or age?
Competing interests
I have used the OIDP among spanish population

subset: commoncrawl


text:
VIDEO: PES 2011 gameplay glimpses
Konami has released this preview video of the latest instalment of the massively popular Pro Evolution Soccer series, PES 2011.
The trailer shows off a few of the new features in the game, including a completely revamped tactics area, with new systems and style commands.
There are examples of an all-new power gauge system which lets you choose the exact strength and position of every pass, with 360 degrees passing now an option.
Defending has also been improved, you can now adopt defensive hold-up play, where your defenders jostle the attackers rather than dive right in with a reckless tackle a la John Terry.
The skills and movements that players can do now have been massively increased - there are 100 new motions in total. Feints and tricks can be mapped on to the R3 button in advance to create patterns of play, but presumably only good players can do all of the tricks on offer (don't bother trying to do step overs with Emile Heskey for example).
The attached screenshots give a glimpse of the new Stadium Edit mode, that allows you to customise your own home ground to play in and there's also a look at the first screen-grabs for the massively reworked Become a Legend mode.
PES 2011 is due out in the autumn (22 October has been mooted as a probable release date) and will be available on Wii, PS3, PS2, PSP, Xbox 360 and PC.
Konami will be hoping that the 2011 version of the purists' favourite title puts the game back ahead of EA's Fifa series. It's widely accepted that Fifa was the winner of the 2010 football sim franchise battle.
Halo 5 limited edition Xbox One controllers now available: This is what they look like
Watch first trailer for episode one of Minecraft: Story Mode, coming this month
Best Windows 10 tablet for playing Xbox One? The Linx Vision is a bargain at £149
PS4 System Software 3.0 Kenshin coming tomorrow, what will you get?
- Halo 5 limited edition Xbox One controllers now available: This is what they look like
- Watch first trailer for episode one of Minecraft: Story Mode, coming this month
- PS4 System Software 3.0 Kenshin coming tomorrow, what will you get?
- Project Spark for Xbox One and Windows goes completely free from 5 October
- Lego Dimensions review: Everything Is Awesome
- Lego Dimensions wave 1 in pictures: The Starter Pack, Team Packs, Level Packs and Fun Packs in the flesh
- Pro Evolution Soccer 2016 review: PESses all over FIFA
- Star Wars: Battlefront beta will be open to all in October, reveals EA
- Assassin's Creed Syndicate preview: In-depth play promises glorious return to form
- Skylanders SuperChargers review: Turbocharging toys-to-life
- When is Android 6.0 Marshmallow coming to my phone?
- Samsung Galaxy View is an iPad Pro rival with a crazy 18.5-inch screen, amazing leaked specs reveal all
- Microsoft October 2015 launch event: What devices to expect
- Master HTML5 and CSS3 web design for 81 per cent off
- Microsoft Lumia 550: What's the story so far?
- Apple buys AI speech startup that could make Siri sound more natural
- Microsoft Lumia 950 and Lumia 950 XL: What's the story so far?
- Microsoft Surface Pro 4: Release date, rumours and everything you need to know
- Watch the final trailer for Spectre here, ahead of film's 26 Oct release
- Microsoft Lumia 950 (Talkman) vs Microsoft Lumia 950XL (Cityman): What's the difference?


text:
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On est allé pour le karaoké du vendredi soir et c'était super le fun!
karaoké with ray!
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Bar Le Ritz P.D.B.
Music Venue
179 rue Jean-Talon Ouest (entre Alexandra & Waverly)
"Awesome venue! Awesome service!"
Underworld Cabaret
1403, rue Sainte-Élisabeth (Coin rue Sainte-Catherine)
4062 Saint-Laurent Boulevard
"Wednesday traditional jazz with Colin Perry & Blind. Authentic 1920's ragtime and charleston music. Peter Mika, the pianist, is amazing!"
Le St-Laurent Frappé
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"It's a dive-bar, which is what makes it good. You get cheap beer, free pool and it's spacious inside. Great spot to go grab a quick beer and play some pool."
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text:
September/October 2015
Public Health Reports
A Message from the Editor
Frederic E.
Shaw, MD, JD
Surgeon General's Perspectives: Making Communities Walkable for Older Adults
Vivek H.
Murthy, MD, MBA
Bottleneck or Magnifying Glass? Monitoring the Health-Care System's Vital Signs through Emergency Departments
Kori Sauser, MD, MSc
Katherine Diaz Vickery, MD, MSc
Matthew M.
Davis, MD, MAPP
Trends and Differences Among Three New Indicators of HIV Infection Progression
Qian An, PhD
Ruiguang Song, PhD
Angela Hernandez, MD
H. Irene Hall, PhD
From the Schools and Programs of Public Health: A Model for Development and Delivery of a Graduate Course in Transdisciplinary Research
Silje E.
Reme, PhD
Alberto J.
Caban-Martinez, PhD
Justin Young, PhD
Anna Arlinghaus, PhD
Garry Gray, PhD
Who Can Publish?
Faculty members from CEPH-accredited Schools and Programs of Public Health may publish On Academics and On Linkages articles. Students, fellows, and post-graduates (2 years) from CEPH-accredited Schools and Programs of Public Health may publish Student articles.
How Do I Submit for Publication?
Manuscripts are submitted electronically at http://phr.msubmit.net. For detailed submission information please visit http://www.publichealthreports.org/Authors.cfm.
Quality of Submissions
Manuscripts should have a strong public health component that adds to the literature, offers sound methodology and actionable results, and features clear and succinct writing. Other considerations include whether or not the submission discusses a topic of broad public health importance and interest, results that can be generalized, and a recent data set appropriate for the study.
Who Will Review My Submission?
On Academics and On Linkages articles are reviewed peers chosen from a current pool of faculty at CEPH-accredited Schools and Programs of Public Health. Student articles are reviewed by peers chosen from a pool of students, fellows, and post-graduates from CEPH-accredited Schools and Programs of Public Health.
Public Health Reports articles on this site can be viewed with Adobe Acrobat Reader.
If you do not have Acrobat Reader, visit Adobe's website to obtain a copy.
© 2014 Association of Schools and Programs of Public Health. All rights reserved.


text:
Here's the post from Hoodline. It shows part of a letter given to all the tenants at, let's say, 312 Fillmore on Haight.
Can't say that I know the purpose, but it could be to give a heads up to tenants who might wish to replace a roommate under the rules laid out by the San Francisco Rent Board. There's some stuff in there about landlords "unreasonably" withholding consent from existing tenants who want to get a new roomie. Of course there are all kinds of factors that determine who and how many people can live in a unit in rent controlled SF, so it's not impossible that you'd have two people in a one bedroom and then one moves out and another wants to move in. And at that point, that's where incomes and credit scores can become factors. And if the LL says no to a potential new roomie, that's when things can go to the SFRB.
Now if you want to say that this letter means "Make $100k Or Get Out," well that's your right, but I think you're jumping to conclusions. If you want to say that this is a kind of harassment, well, you're going to need a lot more than this to be able to do anything with it. And if you're irritated by this landlord coming into your studio all the time without giving proper notice first, well, the lawgivers in Sacramento didn't exactly specify a penalty for not giving proper notice, so there's not much you can do there either.
(But, by all means, go ask Robert (or whatever his name is) what his intent was. And if he says, "Well, I'm evicting everybody in the building who makes less than $100k," well, then the conclusion you all jumped to was OK fine.)
The proper response here is to ignore the letter and store it away along with all the others.
"Mixed use property – 25 residential, 5 commercial 30 unit, 5-story building
18 studios, 6-one bedrooms & spacious 3 bedroom, 1-1/2 bath penthouse with formal living/dining rooms, extra large kitchen, utility area, fireplace and panoramic views.
Building size: 17,750 sq. ft.
Lot size: 5,980 sq. ft.
Year built: 1925
Zoning: NC2
Parcel #: 0849-020
Current rents are $1800 to $3500 Studio to 1 bedrooms"
Life goes on, in high-rent Frsico, a block from the projects, on Webster…
All right, play us out, Victor Vasquez:
Kool A.D., living contradictory since '83
Arkansas street, like a block from the projects
HP some more blocks from some other projects
To Alameda, so we not by the projects
Now look at me, getting nods for my projects


text:
You are here
King tweets congrats to UAE for hosting 2020 World Expo
By JT - Nov 28,2013 - Last updated at Nov 28,2013
AMMAN – His Majesty King Abdullah on Thursday tweeted his congratulations to the United Arab Emirates (UAE) after Dubai won the right to host the 2020 World Expo.
"We congratulate the #UAE for being selected to host the 'Expo 2020'. A source of pride for all Arabs," the King said on the Royal Court Twitter account @RHCJO
Later on Thursday, the King sent a letter to UAE President Sheikh Khalifa Bin Zayed Al Nahyan congratulating him over Dubai's win, the Jordan News Agency, Petra, reported.
The King also called Sheikh Khalifa and his vice president, Sheikh Mohammed Bin Rashid Al Maktoum, who is also the ruler of Dubai, to congratulate them.
On Wednesday night, Dubai was selected as the venue for the 2020 World Expo, beating the Brazilian city of Sao Paulo, Yekaterinburg in Russia and Izmir in Turkey in a vote by members of the world fair body.
The Gulf commercial hub won the support of 116 out of 164 voting members of the Paris-based Bureau International des Expositions in a final-round run-off against Yekaterinburg. Dubai will be the first Middle Eastern city to host such an event.
Related Articles
Royal Jordanian (RJ) was named one of the top 10 safest airlines in the world in 2013 by AirlineRatings.com.
His Majesty King Abdullah on Friday discussed prospects for further cooperation and the latest developments in the region in a telephone call with Sheikh Mohammad Bin Zayed Al Nahyan, crown prince of Abu Dhabi and deputy supreme commander of the UAE armed forces.
Dubai won the right on Wednesday to host the 2020 World Expo, beating off competition from the Brazilian city of Sao Paulo, Yekaterinburg in Russia and Izmir in Turkey in a vote by members of the world fair body.
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Dissectible Capacitor
Next we have a three-piece dissectible Leyden Jar consisting of two metal cups separated by a glass cup. When charged with the Wimshurst machine, we see by touching it with the shorting rod that it holds a large amount of charge. However, when disassembled, the metal cups can be brought into contact with each other and no spark will be generated. When the jar is reassembled it can then be discharged. This demonstrates that, in this situation, the charge actually resides on the surface of the glass (a dielectric), not on the metal.
Comments (1)
Question: is it important that the glass is in contact with the metal, ie, is there an actual charge transfer, or is the capacitor field inducing a charge separation (polarization) inside the glass? If it is the latter (and physics texts typically offer this as the explanation for the dielectric effect), then it is subtle that the Leyden jars allow a large amount of charge to be collected. If the phenomenon is that the charge flows (separates) via the contact with the metal, then the explanation is more obvious, but not along the lines of what is offered in textbooks.
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NEWS ON SCOUTS JAMBOREE 2015 TranslateRead more
Posted 2nd Jul 2015
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Happy scouting Translate
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..WOOD BADGE COURSE PART3B..JOHOR MALAYSIA 7-9 MAY 2015 AT KEM JUBLI INTAN BT PAHAT MALAYSIA..60 SCOUTLEADERS ATTEND THE COURSE WITH PKK-PM-PR. TranslateRead more
THANKS Translate
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PPM JOHOR..Johor Agoonoree 2015 at Kem PLKN/Sakakap Mersing 29mac-02 apr 2015.300 scoutleaders and boyscout attended..this is special,handicapped boysscout having games,campfire,hiking,xpdc,yacht,marching.etc..real skill adventure to them.cheer n thanks to us as trainer. TranslateRead more
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text:
In Santo Domingo we were able to assist a children's program in the trash dump community by building a protection/barrier fence from the road so that the kids can play safely at the facility.
In Santiago, we worked on the second floor of the technical school and assisted in building the perimeter fence around the future aquaponics training center.
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text:
Simon Cowell gets over-25s as X Factor judges' duties revealed
The X Factor judges have been given their categories - and it looks like Simon Cowell is slightly disappointed with his chosen group.
The X Factor judges have been given their categories - and it looks like Simon Cowell is slightly disappointed with his chosen group.
With what most people would probably assume is quite an unVanlike utterance, Mr Morrison released a statement a couple of years back to tell us how delighted and honoured he was to receive the Freedom of his home city. "Belfast is my home", he said.
Joy Beverley's family has paid tribute to "the most wonderful woman" after the singer died at the age of 91.
Bono has written dozens songs during his long and enduring career.
Singer Ellie Goulding was forced to plead with music fans after scuffles broke out during her appearance at a gig in Glasgow.
The almost comically temperamental weather matched the artist at the first of the recently knighted Van Morrison's 70th birthday concerts on Belfast's Cyprus Avenue.
On the magical tree-lined east Belfast street which fired up his youthful dreams, Van the 70th birthday Man turned the tables on thousands of his fans from 18 different countries yesterday by giving them the unforgettable gifts of two of the most remarkable concerts he has...
Game of Thrones has made the Guinness Book of Records for the largest TV drama simulcast.
The headliner stage times have been announced for Electric Picnic at Stradbally next weekend and Friday night kicks off with Underworld headlining the main stage.
Van Morrison has celebrated his 70th birthday with once-in-a-lifetime concerts on the east Belfast street he immortalised in his masterpiece Astral Weeks.
It's been just a few hours since Kanye West announced his presidential run at that bastion of serious political debate, the MTV Video Music Awards, but supporters (and savvy e-sellers) are already rallying behind him.
Rap superstar Kanye West railed against awards shows and announced he would run for president in 2020 as he collected MTV's highest honour at the Video Music Awards.
Supermarket giant Tesco is to tap into the rapidly growing vinyl music market this week when it sells the new album by British rock group Iron Maiden.
Rapper Kanye West has announced he is to launch a bid to become president of the United States in 2020.
Irish superstars The Script brought Tennent's Vital 2015 to a spectacular close last night, ending a fantastic weekend for 65,000 music fans.
Singer-songwriter Ed Sheeran will battle it out with top nominee Taylor Swift at the 2015 MTV Video Music Awards tonight.
The Script and Kodaline are set to party in Belfast for Tennent's Vital today and here is all the information you'll need to rock out in style.
Singer Jess Glynne has revealed landing her first number one album is like "an insane dream."
Rarely has a 'Van the Man' gig been as eagerly anticipated as the one set in the place he named one of his best-loved songs after, Cyprus Avenue.
Pink Floyd are to rehome a giant inflatable pig which featured on the cover of one of their hit albums, after the neglected creature was mistakenly listed for auction.
Northern Ireland
Republic of Ireland
Readers Pictures
Readers Pictures


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We are looking for a native portuguese translator with previous experience in Adwords translation and knowledge of online marketing concepts and writing.
He will translate from english to portuguese about 20 adwords ads, following our indications in terms of keywords to use in the translation.
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The Best Goggles of 2015
The better you see, the better you ski. It's that simple.
The better you see, the better you ski. It's that simple.
Feel like you're having a field day, look like you could carve it up with the pros.
Intelligent designs that are up for anything—and so fun to ride that you'll want to take them everywhere.
Hitting the sweet spots of girth and rocker, they'll keep you surfing powder all day.
Our two favorite skate and classic setups.
New combinations of rocker, shape, and materials continue to drive innovation.
Buying new skis this year? Lucky you. We tested the latest designs, and these came out on top—so shop wisely.
Remember the dire Y2K technological apocalypse predictions? If only they had come true. Without sermonizing, here are 10 ways to disconnect the broadband flow of digitized scheiße that's drowning our...
It's rare that the blanched, distended underbelly of the corporate ski industry gets exposed to the skiing public, but that's exactly what's been happening for the past three seasons in the mountains...
There's a ferocious battle for snowsports business being waged right now between these two western states. So who's going to win the Wasatch-Front-versus-Front-Range wintry gear smackdown?
The Ralph Lauren sweaters are just an excuse to wrap ourselves in the illusion of patriotism—and the charade of insourcing.
Shortsighted marketers might be running snowboarding into the ground, but it isn't too late to save the sport
Brain injuries and how the rewards of risk are fueling a catastrophic trend.
The revamped ARVti features a traditional untapered tip, a touch of rocker, and two full sheets of absorbant Titanal. "It's ideal for billy-goating into tight chutes," said one tester.
At lower speeds, you have to muscle these skis around a bit, but when you're going all out, the wood and metal construction and Blizzard's flutter-free Flipcore rocker—see page 30—feel like a long-...


text:
Do you afraid of job interview?
Do you afraid of job interview? I am really fraid of job interview in English)) ahaha
yes ,of course.i need a perfect accent first:)))
really afraid...
I don't want to chat with a stranger.That makes me tension....
Absolutely, I think anyone also feel worry....With me, I'm very afraid even though I have never interviewed :-)
Hello I am afraid also, Recently I took an english interview, I don´t pass I don´t know why but I think that my accent and my pronunciation were very bad in that interview, I could understand everything she says and I could answer all her questions. However, My nervousness hinders my ability to communicate well. M_rk_s is right and I recommend you a web page with some questions and answers http://www.talkenglish.com/Speaking/listInterview.aspx
I hope this helps.
Until now I have never made an english job interview but If It happened right now, I would feel more sure and able to hold and respond to the questions....But My pronunciation will continue to be bad
never anymore, don't need job interviews,I am the my own boss; when i did, i showed them they need me and not the other way around
I think it's very natural to be a bit nervous about job interview. Although you can overcome your frightening by training. Some rehearsals with a friend or teacher can bring you more confidence.
BTW, you can even apply for some job you are not really want to take, but just to exercise your interview skills.
just show your confidence
I do a lot of interviews in English of people who are non-native English speakers. Here are some of my suggestions:
1. A lot of times people mis-understand the question. If you have any doubts about what is being asked, ask for a clarification, or restate the question back to the interviewer.
2. If the interview is in person, sometimes drawing a picture or diagram is good. I had an inteview once that was not going well at all, but the person stopped to draw a picture and demonstrated his understanding of the process so well that we wound up hiring him.
3. When you are speaking, pause occasionally so that if the interviewer needs to break in, they can. If you're nervous, you might just keep speaking for 10 minutes straight. Don't.
4. Rehearse your answers to common questions. Over and over. And then over again.
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- Horoscopes
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New London — When Alden Santiago and his neighbors looked out their Coit Street windows Sunday morning and saw a plow had never come down their street, they grabbed their shovels.
About a dozen residents on this small, one-way street off Washington Street spent all day Sunday digging out the road themselves.
"We did it by hand,'' said Santiago, who lives at 24 Coit St., as he stood in a lane wide enough for one car to pass through.
Domingo Badillo, also of 24 Coit St., was among those who helped. Although he does not have to work today, many of his neighbors do.
"We're trying to help out the working guys,'' he said, leaning on his shovel. "Now everyone can go to work. I feel good."
Angelane Beard, who lives at 18 Coit St., said her street seems always to be last on the plowing schedule.
"But people have to go to work,'' she said, watching her son, who was home from Southern Connecticut State University, toss snow onto mounds that were nearing 5 feet. "We always get together and help each other."
In the afternoon, Mayor Daryl Justin Finizio heard about the residents shoveling and showed up to help.
"Everyone who can, grabbed a shovel,'' he said, of other city employees who were out in their neighborhoods helping out.
Coit Street, Finizio said, is one of about 30 streets in the city that need smaller plows to clear snow.
"We were hit hard by this storm,'' he said. "All the big trucks were keeping the main roads cleared, so these small side streets, dead ends and cul-de-sacs are last."
He added that the 49-member Public Works Department put in 40 hours over the past two days and were sent home to sleep. But the drivers were ordered back in Sunday and were expected to work through the night to clear a path down all streets.
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Former Hartford police officer plans to remove vessel from Crescent Beach


text:
- Late mistakes doom Raiders in loss to Bears Updated: Oct-05-15 7:25 pm
ALAMEDA, California - For coach Jack Del Rio, the latest loss for the Oakland Raiders really boiled down to two plays.
- Browns missing tackles, defense still full of holes Updated: Oct-01-15 5:12 pm
BEREA, Ohio - Browns linebacker Paul Kruger recently saw an unsettling film filled with shocking, ghastly moments.
- Raiders ride triplets to early season success Updated: Sep-30-15 6:26 pm
ALAMEDA, California - The Oakland Raiders have spent most of the past decade searching for big-play options at quarterback, running back and receiver.
- Derek Carr taking advantage of Raiders' receiver depth Updated: Sep-29-15 7:32 pm
ALAMEDA, California - Oakland Raiders coach Jack Del Rio says the recipe for a good quarterback comes down to two things: decision-making and accuracy.
- Raiders, Falcons, Panthers lead early turnarounds Updated: Sep-28-15 4:20 pm
So the Raiders can win on the road - and in the Eastern time zone, too.
- Dead end: Raiders beat Browns 27-20, halt road losing slide Updated: Sep-28-15 2:43 am
CLEVELAND - Derek Carr and Charles Woodson dressed in front of side-by-side lockers. There they were, the new Raiders star and the old one, the future and the future Hall of Fame.
- Carr, Raiders end road skid with 27-20 win over Browns Updated: Sep-27-15 7:45 pm
CLEVELAND - The locker room attendants busily stuffed shoulder pads, helmets and cleats inside large silver-and-black trunks and travel bags for the flight back to Oakland.
- McCown, Browns come up short in 27-20 loss to Raiders Updated: Sep-27-15 7:08 pm
CLEVELAND - There were chants for the backup quarterback, missed opportunities, a crucial penalty and a late comeback that fell short.
- Browns cornerback K'Waun Williams out with concussion Updated: Sep-25-15 3:40 pm
BEREA, Ohio - Browns starting nickel back K'Waun Williams sustained his third concussion in less than a year and will sit out Sunday against Oakland, forcing changes to Cleveland's secondary.
- Raiders WR Seth Roberts makes mark with game-winning TD Updated: Sep-24-15 5:04 pm
ALAMEDA, California - When Seth Roberts watched his old college teammate from Division II West Alabama make the play that decided the Super Bowl earlier this year, it gave him the confidence that maybe he too could succeed in the NFL despite his small-school pedigree.
- Carr looks to build on late comeback win for Raiders Updated: Sep-23-15 7:33 pm
ALAMEDA, California - Fresh off the most productive game of his young career as the starting quarterback for the Oakland Raiders, Derek Carr now wants to do something he hasn't accomplished yet in the NFL.
- Ravens struggling defense looks to rebound vs. Bengals Updated: Sep-23-15 1:30 pm
OWINGS MILLS, Maryland - Missed assignments, breakdowns in coverage and poor tackling.
- Carr's late TD pass rallies Raiders past Ravens 37-33 Updated: Sep-21-15 2:31 am
OAKLAND, California - Minutes after throwing the winning touchdown, Derek Carr handed Jack Del Rio the game ball for his first win as head coach for the Oakland Raiders.
- Carr's late TD pass rallies Raiders past Ravens 37-33 Updated: Sep-20-15 9:10 pm
OAKLAND, California - All Derek Carr wanted after he threw a late interception in a tie game was a chance.
- Seahawks-Packers at not quite the same stakes Updated: Sep-18-15 12:32 am
The Packers probably don't need any extra incentive when facing the Seahawks, particularly with the memory of their fourth-quarter NFC championship collapse in Seattle still fresh and painful.
- Raiders focused on running ball against Ravens Updated: Sep-17-15 7:08 pm
BERKELEY, California - For all the concern over the injury to the throwing hand of Raiders quarterback Derek Carr, the team's inability to run the ball in its season-opening loss to Cincinnati has to be even more troubling.
- Extra work helps Pack's James Jones get quickly up to speed Updated: Sep-16-15 5:56 pm
GREEN BAY, Wisconsin - Late on an occasional weeknight at Lambeau Field, Green Bay Packers coach Mike McCarthy will run into James Jones getting in extra work in the weight room or training room.
- Flacco, Romo top list of small-school QBs starting in NFL Updated: Sep-16-15 3:21 pm
Western Kentucky senior Brandon Doughty led the nation in passing last season and could be the next quarterback from a mid-major school in the NFL. Below is a list of former small-school signal-callers currently starting in the league:
- Raiders sign S Taylor Mays, DL C.J. Wilson Updated: Sep-15-15 7:28 pm
ALAMEDA, California - The Oakland Raiders responded to injuries to three defensive starters by bringing back safety Taylor Mays and defensive lineman C.J. Wilson on Tuesday.
- Bengals spoil Del Rio's debut with 33-13 win over Raiders Updated: Sep-14-15 2:40 am
OAKLAND, California - With so much attention paid to A.J. Green on the outside, Andy Dalton was pleased to get big tight end Tyler Eifert back to control the middle of the field.
- Raiders struggle in Del Rio's debut as coach Updated: Sep-13-15 9:34 pm
OAKLAND, California - The offense didn't take a snap across midfield until the fourth quarter. The defense struggled from the opening drive.
- Bengals spoil Del Rio's debut with 33-13 win over Raiders Updated: Sep-13-15 9:03 pm
OAKLAND, California - Andy Dalton couldn't have scripted his season opener with Cincinnati much better.
- The Latest: Raiders booed off field at halftime vs Cincy Updated: Sep-13-15 6:12 pm
The Latest on the NFL's opening Sunday (all times EDT):
- Raiders QB Derek Carr leaves with injury Updated: Sep-13-15 5:38 pm
OAKLAND, California - Oakland Raiders quarterback Derek Carr has left the opener against Cincinnati with an undisclosed injury.
- Players who could make breakthroughs in 2015 Updated: Sep-10-15 9:33 am
Most of those preseason stars who slalomed their way into the end zone or smashed into ball carriers now get to watch the real elite NFL players take the stage.


text:
41. VCA Wellington Veterinary Hospital
3921 Miller Road, Newtown Square, PA 19073
Welcome to VCA Wellington Veterinary Hospital! We are a full-service veterinary medical facility located in Newtown Square, PA. Our professional and courteous staff seeks to provide the best possible medical, surgical and dental care for our highly-valued patients. We are committed to promotingview details hide details
Services: Veterinary Dentistry, Veterinary Euthanasia, Animal Flea Control, Animal Microchipping, Animal Daycare, Veterinary Vaccinations, Spaying/Neutering, Animal Grooming, Veterinarians, Animal Boarding, Veterinary Surgery
42. The Newtown Veterinary Hospital
107 Penns Trail Newtown, Newtown, PA 18940
We are pleased to offer the convenience of scheduled appointments to our clients and their pets. Although we accept walk-in visits, scheduled appointments will take precedence. All surgical procedures are by appointment only The Newtown Veterinary Hospital has been in operation sinceview details hide details
Services: Veterinary Surgery, Animal Boarding, Veterinary Vaccinations, Declawing, Animal Daycare, Veterinary Dentistry, Veterinary House Calls, Animal Microchipping, Spaying/Neutering, Small Animal Vet, Veterinarians, Animal Flea Control
43. Banfield Pet Hospital® - Fairless Hills
220 Commerce Blvd, Fairless Hills, PA 19030
A great local veterinarian loves your pet (almost) as much as you do by providing the best preventive pet health care. From nose-to-tail veterinary medical exams to vaccinations, microchipping, dental care and surgery, you'll find the vet your pet deserves at your neighborhood Banfield Petview details hide details view deal
Services: Veterinary Euthanasia, Veterinarians, Animal Microchipping, Veterinary Dentistry, Spaying/Neutering, Veterinary Medical Specialties, Holistic Veterinary Medicine, Animal Flea Control, Small Animal Vet, Declawing, Veterinary Surgery
44. Clementon Animal Hospital
210 White Horse Pike, Clementon, NJ 08021
Welcome to Clementon Animal Hospital, the premier provider of complete veterinary care for your pet. Clementon Animal Hospital has been serving Clementon and the surrounding communities since 1965. Our veterinarians have established a reputation for high quality medicine, compassionate care, andview details hide details
Services: Exotic Animal Vet, Emergency Veterinary Clinic, Animal Microchipping, Declawing, Veterinary Surgery, Veterinarians, Veterinary Euthanasia, Veterinary Dentistry, Spaying/Neutering, Animal Flea Control, Reptile Vet, Small Animal Vet
45. Aston Veterinary Hospital
5200 Pennell Rd, Media, PA 19063
Aston Veterinary Hospital has been caring for pets in Aston and Media — and greater Delaware County — for more than 60 years. We are a full-service, AAHA-certified, small animal facility providing professional health care for your pet. Today our knowledgeable veterinarians and dedicated technicalview details hide details
Services: Small Animal Vet, Spaying/Neutering, Veterinary Vaccinations, Animal Microchipping, Animal Boarding, Veterinarians, Animal Flea Control, Veterinary Surgery, Declawing, Veterinary Dentistry, Veterinary Medical Specialties, Veterinary Euthanasia
46. Skippack Animal Hospital
3865 Skippack Pike, Skippack, PA 19474
Skippack Animal Hospital is a full-service, small animal veterinary hospital located in Skippack, PA. The professional and courteous staff at Skippack Animal Hospital seeks to provide the best medical, surgical, and dental care for their highly-valued patients. Committed to promoting responsible petview details hide details
Services: Animal Daycare, Spaying/Neutering, Declawing, Veterinary Vaccinations, Animal Flea Control, Reptile Vet, Veterinary House Calls, Veterinary Euthanasia, Animal Boarding, Small Animal Vet, Animal Microchipping, Veterinary Surgery, Veterinarians, Veterinary Dentistry, Bird Vet, Exotic Animal Vet
47. Indian Walk Veterinary Center
662 Durham Rd, Newtown, PA 18940
Our beautiful and state-of-the-art hospital is located in Wrightstown, PA. Since 1990 we have provided Wrightstown and surrounding areas with a high standard of veterinary care and technical expertise. The scope of our comprehensive care covers: wellness and prevention, vaccinations, dentistry,view details hide details
Services: Veterinary Dentistry, Veterinary House Calls, Declawing, Animal Microchipping, Exotic Animal Vet, Veterinary Surgery, Reptile Vet, Veterinarians, Animal Flea Control, Small Animal Vet, Spaying/Neutering, Veterinary Vaccinations
48. Doylestown Veterinary Hospital
380 North Shady Retreat Rd., Doylestown, PA 18901
The doctors and healthcare team at Doylestown Veterinary Hospital strive to offer the old-fashioned tradition of compassionate care along with modern techniques and medical innovations. At our hospital our goal is to get to know your pets as members of your family, and develop a lastingview details hide details
Services: Veterinarians, Animal Grooming, Veterinary Dentistry, Spaying/Neutering, Declawing, Veterinary Surgery, Veterinary Medical Specialties, Animal Microchipping, Veterinary Euthanasia, Veterinary Docking, Veterinary Vaccinations, Animal Flea Control
49. VCA Delaware Valley Animal Hospital
266 Lincoln Highway, Fairless Hills, PA 19030
VCA Delaware Valley Animal Hospital has been offering veterinary services to our community since 1954. We are a full-service hospital located in Fairless Hills, Pennsylvania, near the Oxford Valley Mall. Our team of experienced professionals is dedicated to offering the utmost in veterinary care. Weview details hide details view deal
Services: Veterinary Surgery, Small Animal Vet, Exotic Animal Vet, Animal Microchipping, Veterinary Vaccinations, Animal Flea Control, Declawing, Veterinarians, Veterinary Euthanasia, Holistic Veterinary Medicine, Spaying/Neutering, Veterinary Dentistry
50. Banfield Pet Hospital® - Mantua
637 Woodbury Glassboro Rd, Sewell, NJ 08080
A great local veterinarian loves your pet (almost) as much as you do by providing the best preventive pet health care. From nose-to-tail veterinary medical exams to vaccinations, microchipping, dental care and surgery, you'll find the vet your pet deserves at your neighborhood Banfield Petview details hide details view deal
Services: Veterinary Euthanasia, Holistic Veterinary Medicine, Animal Flea Control, Animal Microchipping, Veterinarians, Small Animal Vet, Spaying/Neutering, Veterinary Medical Specialties, Veterinary Dentistry, Veterinary Surgery


text:
|Reviews for gii,takumi and baby makes three
| tuyet chapter 5 . 5/8
please update soon it getting good
| Zuzanny chapter 5 . 12/5/2014
I'm sorry, i enjoy mpreg very much (usually), but my realitymeter just couldn't be suspended enough. No Takumi isn't pregnant. He just has testicular cancer. (That is what a positive urine based pregnancy test picks up in men). I hope he gets some help for that real quick!
I would find it interesting to read to have everyone running around thinking that he is pregnant, only to discover the devastating truth. How would Gii be able to handle it?
| Guest chapter 5 . 10/25/2014
Looking forward 4 next update.
| didi-chan chapter 5 . 10/16/2014
love it keep going
| Awesome guest chapter 5 . 9/18/2014
Yay gii found him! Can't wait for net update! 3
| Springmiya chapter 5 . 9/13/2014
So happy be found him _ can't wait for your next update... so happy
| aeiritz chapter 5 . 9/14/2014
Finally new chapter...thanks for update...looking forward to next chapter...:))))
Can't wait...
| ceciflo chapter 5 . 9/14/2014
Oh my God,
A new chapter,thank you for this update
It's good to see that Gii found Takumi.
| xXlovelyXx chapter 4 . 6/12/2014
Can't wait to read more! Love this! :)
| DAIMAOOAMIAD chapter 4 . 5/22/2014
this is rare... ;-) love it.. hope to read more of the new chapter... really want to know what happen to Takumi... is he really pregnant?... interesting... keep on writing ok...
| aeiritz chapter 4 . 4/7/2014
Kyaaaa finally, thanks for update. I like ur story. Hope it's not long for ur update next chapter. Can't wait for next chapter. Thanks again...o
| AoryutochanZ chapter 4 . 3/23/2014
hwaa... so interesting! xp can't wait for the next chapter.. xp
btw.. about gii's friend name.. his name is Akaike Shouzo
| Elmanime chapter 3 . 3/13/2014
You need to continue the story. I'm going crazy not knowing what happen next . Please
| Guest chapter 3 . 9/28/2013
Wears chapter 4 at i want to now what happens next.
| Irene.Hansz chapter 2 . 4/26/2013
its a new twist story. but i like it. plez update this story


text:
Hotel information
Hotel facilities
- Reception (lobby)
- Elevator
- Public Internet terminal
- WLAN with Internet access in lobby
- Total number of rooms: 96
Room facilities
- Cable TV
- TV remote control
- Telephone by the bed
- Telephone in the bathroom
- TV with international news channel
In-house services
- Restaurant(s) 1, open from 12:30 PM.00 until 3:00 PM.00 and from 7:30 PM until 10:30 PM.00, Closed
- Hotel bar
- Café/bistro
- Breakfast from 7:00 AM o'clock to 10:00 AM o'clock
- Breakfast for early risers from 5:00 AM o'clock to 7:00 AM o'clock
Show all
Style of hotel and ambience
The NH Buenos Aires Crillón hotel combines an avant-garde style with French architecture and invites its guests to relax. Business guests will appreciate the free Wi-Fi access and the modern conference rooms. After a restful night in your elegant room, you can start your day with a buffet-style breakfast.
Hotel details
Total number of rooms: 96, Number of single rooms: 96, Number of double rooms: 96, No-smoking room: 96,
Service times
Reception open:
00:00 - 24:00
Reception manned at weekends:
00:00 - 24:00
Earliest check-in:
Latest check-out:
Accepted payment methods
Diners Club
American Express


text:
Book your room at Motel 6 Grande Prairie Ab
Standard Room, 1 Queen BedMax Occupancy: 2 guests (up to 1 child, 1 infant)
Standard Room, 1 Queen Bed, AccessibleMax Occupancy: 2 guests (up to 1 child, 1 infant)
Standard Room, 2 Double BedsMax Occupancy: 4 guests (up to 3 children, 2 infants)
Get an overview of this hotelFamily-friendly motel in Grande Prairie with free parking
This family-friendly Grande Prairie motel is located near the airport, within 3 mi (5 km) of County of Grande Prairie No.1, Prairie Mall Shopping Centre and Clairmont Community Centre and Arena. Gateway Power Centre and Crystal Centre are also within 6 mi (10 km).
Property Features
Along with coffee/tea in the lobby, this motel has dry cleaning and laundry facilities. Free WiFi in public areas and free self parking are also provided. Additionally, a 24-hour front desk, barbecue grills, and a picnic area are onsite.
Room Amenities
All 132 soundproofed rooms feature free wired Internet and Select Comfort beds. For a bit of entertainment, plasma TVs come with cable channels, and guests can also appreciate conveniences like refrigerators and microwaves.Information missing or incorrect? Tell us!
Hotel Amenities
Hotel Amenities
Motel 6 Grande Prairie Ab features barbecue grills, a picnic area, and coffee/tea in the lobby. High-speed wired and wireless Internet access is complimentary. This family-friendly motel also offers laundry facilities, dry cleaning/laundry services, and ATM/banking services. Onsite self parking is complimentary.
Motel 6 Grande Prairie Ab has designated areas for smoking.
- 24-hour front desk
- ATM/banking
- Barbecue grill(s)
- Coffee/tea in lobby
- Designated smoking areas
- Dry cleaning/laundry service
- Elevator/lift
- Free RV, bus, truck parking
- Free self parking
- Free WiFi
- Free wired high-speed Internet
- Laundry facilities
- Number of buildings/towers - 1
- Number of floors - 4
- Picnic area
- Television in lobby
- Total number of rooms - 132
- Year Built 2008
Family Friendly Amenities
- Free Wi-Fi
- Laundry facilities
- Microwave
- Refrigerator
- Soundproofed rooms
Available in all rooms: Free wired high-speed Internet
Available in some public areas: Free WiFi , Free wired high-speed Internet
Free self parking, Free RV, bus, truck parking
Room Amenities
- Air conditioning
- Blackout drapes/curtains
- Cable TV service
- Climate control
- Connecting/adjoining rooms available
- Daily housekeeping
- Desk
- Free local calls
- Free wired high-speed Internet
- Hair dryer (on request)
- Iron/ironing board (on request)
- Microwave
- Phone
- Plasma TV
- Premium bedding
- Premium TV channels
- Private bathroom
- Refrigerator
- Shower/tub combination
- Sleep Number by Select Comfort mattress
- Soundproofed rooms
Nearby Things to Do
The recreational activities listed below are available either on site or nearby; fees may apply.
- Golfing nearby
- Downhill skiing nearby
- Cross-country skiing nearby
- Snowboarding nearby
- Snowmobiling nearby
- Hiking/biking trails nearby
- Ski lessons available nearby
- Ski equipment rental shops nearby
- Golf lessons available nearby
To make requests for specific accessibility needs, complete the "Special or Accessibility Requests" section of "Trip Preferences" when you book your hotel.
- Accessible path of travel
- Accessible bathroom
- Roll-in shower
- Accessible parking
- In-room accessibility
Hotel Policies
Check-in time starts at 3 PM
Minimum check-in age is 18
Check-out time is 11 AM
Payment types
Children and extra beds
- Children are welcome.
- Kids stay free! Children under 17 years old stay free when using existing bedding.
Pets allowed
You need to know
Extra-person charges may apply and vary depending on hotel policy.
Government-issued photo identification and a credit card are required at check-in for incidental charges.
Special requests are subject to availability upon check-in and may incur additional charges. Special requests cannot be guaranteed.
No rollaway/extra beds available
No cribs (infant beds) available
We should mention
Children 17 years old and younger stay free when occupying the parent or guardian's room, using existing bedding. The property has connecting/adjoining rooms, which are subject to availability and can be requested by contacting the property using the number on the booking confirmation.


text:
A Flawed Program, Overwhelmed
By Mac William Bishop, Channon Hodge, Stephen Farrell and Pedro Rosado | Nov. 13, 2012 | 13:14
TimesCast: The government's flood insurance program is at risk of running out of money. | Two weeks after Sandy, waiting for aid and losing patience. | Leaving Staten Island's devastation behind.
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